Method of reactivating reduced metal oxide catalysts



Patented Mar. 14, 1950 UNITED STATES PATENT OFFICE METHOD OF REACTIVATING R EDUCED METAL OXIDE CATALYSTS John w. Teter, Chicago, Ill., assignor to Sinclair g Company, New York, N. Y., a corpora tion of Maine No Drawing. Application October 12, 1944. Serial No. 558,483

particularly propylene and ethylene, in the presence of a catalyst which selectively favors the amination reaction are described in applications Serial No. 289,186, flied August 9, 1939,-

abandoned, Serial No. 365,561, filed November 13, 1940, now U. S. Patent No. 2,381,470, Serial No. 444,094, filed May 22, 1942, now U. S. Patent No. 2,418,562, and Serial No. 464,636, filed November 5, 1942, now U. S. Patent No. 2,381,709.

In general, the process is carried out by bringing the olefin and ammonia into contact with a catalyst, e. g., a fixed bed catalyst, at high temperatures and pressures, for example, at temperatures of 450 to 750 F. and at high pressures, for galilnple, 500 to 3000 lbs. pressure per square Catalysts which are useful in the process are the reduced metal oxides, such asnickel, and cobalt, particularly cobalt, deposited on a suitable carrier. Cobalt promoted by manganese deposited ona carrier such as diatomaceous earth,

cobalt silicate, etc., is a particularly advantageous catalyst. Such catalysts are described in applications Serial Nos. 444,095, abandoned, 444,096, now U. S. Patent No. 2,406,929, and 444,097, now U. S. Patent No. 2,398,899, filed May 22, 1942, and Serial No. 489,087, filed May 29, 1943, now U. S. Patent No. 2,381,473.

The amination reaction is accompanied by side reactions, including cracking, dehydrogenation,

polymerization, etc. In the course of the reaction heavy, tarry or carbonaceous materials are formed to some extent and a considerable proportion of such material as is formed is deposited on the catalyst. Whether because of this or for some other reason, the catalyst loses its activit after being on stream for a considerable period, and requires reactivation. The present invention is directed to improvements in the reactivation operation which permit reactivation to be accomplished rapidly, so that the off-stream time required for reactivation is a minimum, and which result in a reactivated catalyst of activity comparable to a fresh catalyst and in a prolonged ultimate useful life of the catalyst.

In accordance with the present invention, the catalyst is reactivated by the use of hydrogen at high temperatures and pressures, and with purging of the catalyst with ammonia or an inert gas at the end of reactivation and before bringing the catalyst back on-stream.

The reactivation results in the substantial removal of the tarry or carbonaceous material which is deposited on the catalyst in the course of the amination reaction, apparently convertin: it to hydrocarbon, largely methane, and ammonia. The tarry or carbonaceous material which is deposited on the catalyst appears to consist largely oi. polymeric or high molecular nitrogen-containing compounds and the treatment with hydrogen at high pressures and high temperatures, in the presence of the catalyst, results in the hydrogenation or hydrogenolysis of this high molecular weight material with production of hydrocarbon, largely methane and ammonia. It should be noted that the ammonia produced is not the result oi the simple release oi adsorbed or otherwise physically bound ammonia, because purging of the catalyst with inert gases or the like does not result in the removal of this ammonia from the catalyst.

. By the use of the present invention, a catalyst which has started to lose activity in the course of the direct amination reaction may be effectively reactivated in a relatively short period of time, for example, 6 hours or less, and through this rapid reactivation of the catalyst, it is possible to operate the amination process, with two reactors in parallel, substantially continuously with one reactor on-stream while the catalyst in the other is being reactivated. v

The temperature at which the reactivation is carried out may be varied within substantial ranges, but advantageously, reactivation is carried out at about the temperature which is used in the amination reaction. This temperature may range, as pointed out above, about 450 to about 750 F. A very good temperature range for the amination of propylene appears to be about 640 to 650 F., and in such a procedure, reactivation can be advantageously carried out at about the same temperature. Somewhat lower temperatures than those used in the proccss may be used, because the reactivation is an exothermic reaction, apparently, as pointed out above, involving hydrogenation or hydrogenolysis.

Similarly, the pressure used in the hydrogenation can be varied over a considerable range. Thus it may be carried out at 1000 or 2000 lbs. pressure or higher. Lower pressures may be used. A pressure of about 3000 lbs. is advantageously used as it permits eilective reactivation of the catalyst in the period of about 4 hours.

that is, a period of exposure of the catalyst to the high pressure, high temperature hydrogen of about 4 hours, corresponding to a total period required'for reactivation, including the times required for pressure reductions and pur ing. of about 6 hours or less. The use of such an interval-for reactivation is advantageous, because it corresponds to an on-stream period during which the catalyst maintains high activity. While the catalyst can be used on-stream for considerably longer times than 6 hours and still give good yields of nitrogen-containing products, there is no great advantage in such long continued onstream periods in view of the rapidity and effectiveness of the reactivation when carried out in accordance with this invention.

For example, in the production of nitrogencontaining products by the direct amination of propylene, using a cobalt catalyst of the. type described in the applications previously referred to, the amination may be carried out at a pressure of about 1500 lbs. and a temperature of I about 640 to 650 F., the gas mixture being preheated and then fed to the catalyst-chamber. Frequently, after about 6 hours of operation, the catalyst activity shows signs of falling oif, and the supply of reactants to the reactor is cut oif. The reactor is thenireleased to atmospheric pressure, taking such steps as are desirable to recover whatever materials of value are in thereactor, and hydrogen is introduced into the reactor to reactivate the catalyst. The hydrogen will be preheated to about 600 to 650 F. and introduced at that high temperature. As the reaction is exothermic, adiabatic conditions may be maintained in the reactor, that is, it is unnecessary to supply extraneous heat. The operations of reducing the initial pressure, introducing the hydrogen and building up to the hydr gen pressure, for example, to about 3000 lbs., may

take about one hour. Hydrogen at the pressure of 3000 lbs. per square inch and a temperature of BOO-650 F. is then passed slowly through the reactor for a period of about 4 hours. In the course of this time. reactivation of the catalystis substantially completed, much or all of the tar or carbonaceous material being removed from the catalyst and converted to hydrocarbon and ammonia. At the end of this reactivation period, the hydrogen pressure in the reactor is released, and the reactor is purged with ammonia, to remove hydrogen and so prevent hydrogenation of the un-' saturated portion of feed at the'start of the on-stream period. After purging with ammonia, the reactor is brought back on-stream and the amination process proceeds. The time required for the release of thehydrogenprcssure and the ammonia purging may be about $6 to hour. Instead of ammonia, inert gases, such as nitrogen or the like may be used to remove the hydrogen from the reactor. Ammonia is conveniently used because it is one of the reacting materials and because, it is important wheneverhydrocarbon is introduced into the reaction vessel at high temperatures, the ammonia be present to prevent cracking and formation of coke or the like which would impair the activity of the catalyst.

I claim:

1. In a process for reactivating a catalystcontaining as its essential active ingredient a reduced oxide of a metal selected from the group consisting of cobalt and nickel, said catalyst carrying a nitrogen-containing tarry material deposited thereon during the reaction of ammonia with oleflns in an operation wherein a mixture of ammonia and olefin is brought into contact with said reduced metal oxide catalyst at a temperature within the range of 450-750 F. and at a pressure within the range 500-3000 pounds per square inch, the improvement which comprises passing hydrogen at a temperature approximating 450-750 F. and at a pressure approximating 1000-3000 pounds per square inch in contact with said catalyst, whereby the tarry material is converted to'volatilized hydrocarbon and ammonia and the catalyst is reactivated.

2. The process as in claim 1. in which, after reactivation and before being brought back onstream, the catalyst is purged of hydrogen by passing ammonia over it.

' i JOHN W. TETER.

REFERENCES CITED The following references are of record in the file of this patent:

. UNITED STATES PATENTS Number Name Date 1,121,860 Moore Dec. 22, 1914 1,210,367 Reynolds Dec. 26, 1916 1,320,039 Ellis ...'.1 Oct. 28, 1919 1,483,412 Clancy Feb. 12, 1924 1,489,497 Larson Apr. 8, 1924 2,225,782 Ipatieff et a1. Dec. 24, 1940 2,238,726 Feisst et al. Apr. 15, 1941 2,289,731 Roelen et al. July 14, 1942 2,294,414 Matuszak et al Sept. 1, 1942 2,360,787 Murphree et a1. Oct. 17, 1944 2,386,032 Campbell. Oct. 2, 1945 Teter Apr. 22, 1947 

1. IN A PROCESS FOR REACTIVATING A CATALYST CONTAINING AS ITS ESSENTIAL ACTIVE INGREDIENT A REDUCED OXIDE OF A METAL SELECTED FROM THE GROUP CONSISTING OF COBALT AND NICKEL, SAID CATALYST CARRYING A NITROGEN-CONTAINING TARRY MATERIAL DEPOSITED THEREON DURING THE REACTION OF AMMONIA WITH OLEFINS IN AN OPERATION WHEREIN A MIXTURE OF AMMONIA AND OLEFIN IS BROUGHT INTO CONTACT WITH SAID REDUCED METAL OXIDE CATALYST AT A TEMPERATURE WITHIN THE RANGE OF 450*-750*F. AND AT A PRESSURE WITHIN THE RANGE 500-3000 POUNDS PER SQUARE INCH, THE IMPROVEMENT WHICH COMPRISES PASSING HYDROGEN AT A TEMPERATURE APPROXIMATING 450*-750*F. AND AT A PRESSURE APPROXIMATING 1000-3000 POUNDS PER SQUARE INCH IN CONTACT WITH SAID CATALYST, WHEREBY THE TARRY MATERIAL IS CONVERTED TO VOLATILIZED HYDROCARBON AND AMMONIA AND THE CATALYST IS REACTIVATED. 